EP1243691A1 - Verfahren zur Herstellung eines mikrofasrigen, wildlederähnlichen Vliesstoffes - Google Patents

Verfahren zur Herstellung eines mikrofasrigen, wildlederähnlichen Vliesstoffes Download PDF

Info

Publication number
EP1243691A1
EP1243691A1 EP02004291A EP02004291A EP1243691A1 EP 1243691 A1 EP1243691 A1 EP 1243691A1 EP 02004291 A EP02004291 A EP 02004291A EP 02004291 A EP02004291 A EP 02004291A EP 1243691 A1 EP1243691 A1 EP 1243691A1
Authority
EP
European Patent Office
Prior art keywords
woven fabric
component
sea
preparation
suede
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP02004291A
Other languages
English (en)
French (fr)
Other versions
EP1243691B1 (de
Inventor
David Latini
Gianni Romani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Alcantara SpA
Original Assignee
Alcantara SpA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alcantara SpA filed Critical Alcantara SpA
Publication of EP1243691A1 publication Critical patent/EP1243691A1/de
Application granted granted Critical
Publication of EP1243691B1 publication Critical patent/EP1243691B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
    • D06N3/14—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with polyurethanes
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
    • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
    • D06N3/0002—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate
    • D06N3/0004—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof characterised by the substrate using ultra-fine two-component fibres, e.g. island/sea, or ultra-fine one component fibres (< 1 denier)
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
    • Y10T442/2352—Coating or impregnation functions to soften the feel of or improve the "hand" of the fabric

Definitions

  • the present invention relates to a process for the production of synthetic microfibrous non-woven fabric of the so-called suede-finish type that does not require the use of organic solvents, but that allows a product with optimal physical-mechanical and "hand" characteristics to be obtained.
  • a fiber of the "islands in the sea” type is prepared from two components by feeding two polymers to a die-plate in such a way that one of the components -- "sea" -- completely surrounds several filaments of the other constituent -- "islands".
  • the "sea” component is generally polystyrene (PST) or another polymer that has such spinning characteristics as to wrap itself around the microfibers of the "islands” component and is moreover easily soluble in normal organic solvents.
  • the "sea” component is polyethyleneterphthalate (PET).
  • a felt is prepared with the fiber thus obtained, by means of drawing; it is impregnated with an aqueous polyvinylalcohol solution (PVA), the "sea” component is dissolved in trichloroethylene (“trielene”), the felt is impregnated with a polyurethane solution (PU) in dimethylformamide (DMF) and, finally, the PVA is eliminated.
  • PVA polyvinylalcohol solution
  • PU polyurethane solution
  • DMF dimethylformamide
  • the bond between PU and microfiber is stronger and, consequently, all the physical-mechanical characteristics - and the abrasion resistance above all - are better.
  • the present invention proposes to overcome all the aforementioned disadvantages.
  • the present invention relates to a process for the production of microfibrous non-woven fabric of the suede-finish type that does not use organic solvents which introduce a high cost of recovery and disposal, enabling the production of products with chemical-physical characteristics substantially equal if not superior to those of the products of the known art.
  • microfibrous non-woven fabric of the suede-finish type that comprises the following stages:
  • the "islands" component could be constituted by polyethyleneterphthalate or modified polyesters, cationic polyesters, nylon or other types of polyamides, from polyethylene, polypropylene or other types of poliolefine.
  • Figure 2 shows a simplified block outline of the process according to the invention for the production of non-woven fabric.
  • the "sea” components could be constituted by nylon or other polyamides, modified polyesters and, in a generalized manner, other polymer fibers with the essential characteristic of being soluble in " ecologically clean " solvents, preferentially in acidic or alkaline aqueous solutions.
  • the ratio between the "island” component and the “sea” component used in the spinning bi-component must be within the range 20/80 and 80/20.
  • the polyvinylalcohol employed in the process of the present invention in order to impregnate the bi-component fiber felt must have solubility in water or the aqueous solvents used for its removal, significantly lower than the solubility of the "sea" component of the bi-component fiber.
  • Such lower solubility can be intrinsic of the polymer or can be created after impregnation by means of hot treatments successive to the impregnation or by adding compounds that can cause a reticulation of the polyvinylalcohol.
  • a polyvinylalcohol must be used with high saponification index, typically superior to 95% and, preferably, superior to 99.5%.
  • This polyvinylalcohol has a high degree of crystalinity and a much lower viscosity (at 25°C, a 12% solution must have a viscosity in the range 100 to 300 mPas and at 20°C, a 4% solution must have a viscosity in the range 10 to 16 mPAs).
  • the lower solubility of the polyvinylalcohol can also be obtained by means of treatment of the polyvinylalcohol after impregnation, as stated above.
  • One way to render the polyvinylalcohol more difficult to remove in the course of removing the "sea" component is by treating the impregnated felt at high temperature, in the range 150° to 200°C, for a period of time between 5 and 40 minutes.
  • Another way of rendering the polyvinylalcohol more resistant to the "sea" component removal treatment is to add a cross-linking"cross-linker" (chosen from boric acid H 3 BO 3 , or zirconium or vanadium compounds such as triethanolamine zirconate or vanadate - boric acid being preferred) to the of PVA impregnation solution in amounts ranging from 0,5% to 7 % with respect to PVA, and preferably between 1% and 5%.
  • Both methods described above can also be used to reduce the solubility of the Polyvinylalcohol and prevent its removal in the course of the "sea" component removal treatment.
  • the addition of cross-linkingagents - boric acid in particular - reduces the solubility of the polyvinylalcohol in an alkaline environment, while the extraction in an acid environment is not substantially modified.
  • the impregnation of the felt with polyurethane after the elimination of the "sea” component can be achieved by addition of dimethylformamide or dimethylacetamide PU solution, analogous to what happens in the conventional systems indicated above, or, preferably, with polyurethane impregnation in emulsion or aqueous dispersion. If the process with polyurethane in emulsion or aqueous dispersion is used, it is necessary that the bond between the polyurethane and felt and the polyurethane itself can resist the extraction of the polyvinylalcohol. For this purpose, analogous to what happens for polyvinylalcohol in the extraction of the "sea" component, it is necessary to fix the polyurethane so that it can resist the treatment of the felt in order to extract the polyvinylalcohol.
  • the impregnation of the polyurethane can take place by means of the addition of cross-linkingagents known in the art which, according to the type, are active at ambient temperatures or relatively high temperatures (110°-200°C).
  • the impregnated felt is therefore treated with warm water preferably in a vibro-washer at temperatures in the range 50° to 110°C, and preferably between 85° and 95°C.
  • the pH of the solution will have to be in the range 3 to 7.
  • a bi-component fiber is spun through a die-plate very well known to one skilled in the art, and that it enables a compound fiber to be obtained in which one of the polymers is arranged around the elementary fibers of the other polymer.
  • the fiber thus obtained is treated according to finishing methods known in the art of spinning; in particular, the bi-component fiber, before spinning, must have a denier rating in the range 10 to 13 denier, preferably in the range 11 to 12.5 denier.
  • Drawing is executed with draw-ratios that generally vary in the range 2 to 5, and preferably in the interval 3 to 4, with a final denier rating of the bi-component compound fiber between 2 to 6 denier and the denier rating of the component "islands" within the range 0.08 - 0.5 denier.
  • a bi-component fiber consisting of polyethyleneterphthalate as "island” component, and a modified polyester soluble in an alkaline aqueous solution, as "sea” component.
  • Said “sea” component consists of PET-5-sodiosolfo-isoptalic acid ethylenglicol ester, hereinafter referred to as TLAS.
  • a felt is prepared with such bi-component fiber by drawing; the apparent density of the felt, (after dimensional stabilization by heat treatment with warm water or warm air, or directly in hot PVA impregnation solution) must be, preferentially, in the range 0.1 to 0.5 g/cm 3 , more preferably in the range, 0.15 ⁇ 0.4 g/ cm 3 , with thickness still in the range 2 to 4 millimeter, in order to obtain a final non-woven fabric with good softness.
  • the felt thus obtained is impregnated with an aqueous polyvinylalcohol solution (PVA), with a concentration in the range 5% to 30% preferably in the range 8% to 15%, more preferably between 10% and 13%, and at a temperature in the range 60° to 90°C.
  • PVA polyvinylalcohol solution
  • the PVA used in the present invention must have a higher degree of crystalinity, a saponification value in the range 85% and 100%, preferably superior to 99.5%, and a very low viscosity (at 25°C, a 12% solution must have a viscosity in the range 100 to 300 mPA ⁇ s and at 20°C, a 4% solution must have a viscosity in the range 10 to 16 mPA ⁇ s).
  • the high saponification rate polyvinylalcohol is referred to below simply as H.S.PVA.
  • the H.S.PVA applied to the felt in this stage must subsequently resist the drastic conditions of dissolving the "sea" component, for which it needs to be subjected, as well as normal drying, to an thermo-fixing or curing treatment at high temperature, in the range 150° to 200°C, for a time in the range 5 to 40 minutes.
  • the H.S.PVA in the section of the non-woven fabric is present for the greater part in the surface and, to a lesser extent, the central zone.
  • Figure 3 shows the distribution of the H.S.PVA across the thickness of the non-woven fabric according to the invention after dissolving the "sea" component.
  • an amount of boric acid H3BO3 varying in the range 0.5% to 10 % and preferably between 1% and 5% with respect to the PVA is used as cross-linker of the H.S.PVA, and is added to the H.S.PVA impregnation solution.
  • a definite amount of H3B03 may be added to the alkaline bath used for the removal of sea component after PVA impregnation and fixing phase.
  • a treatment is carried out with an aqueous sodium hydroxide solution, with a concentration in the range 1% to 15% and at a temperature of between 40° and 90°C; the time to dissolve the " sea “ component varying according to the conditions, from 4 to 40 minutes.
  • the dissolving conditions are optimized in order to dissolve the "sea” component in the shortest possible time and, in such time, to dissolve the smallest possible amount of applied H.S.PVA while avoiding any significative PET microfiber deterioration.
  • the piece is subsequently washed abundantly with water at room temperature, to remove the soda residue remaining impregnated in the non-woven, thus preventing partial dissolving of the "islands" component.
  • the non-woven fabric from which the "sea" component has been extracted is impregnated with polyurethane dispersed in aqueous emulsion, at room temperature, with a concentration varying between 10% and 20 %, and it is dosed on the piece through suitable spreader rollers to obtain a in the final product a PU concentration of 25 to 45%, preferably 30 to 40%.
  • a portion of PU may be added to the piece before submitting it to the alkaline treatment to remove the sea component in order to improve the piece resistance against the above alkaline treatment as well as the physical and mechanical characteristics of the final product.
  • the polyoils that constitute polyurethane (PU) can be of polyether type, polyester type, polycarbonate type and polyester-polycarbonate type; the PU can be prepared using one or more of such types of polyoils that must have an average molecular weight in the range 500 to 5000.
  • the di-isocyanates used for the synthesis of the PU could be aliphatic or aromatic; chain extenders generally used, instead, are low molecular weight molecules that possess two or more active hydrogens that can react with the isocyanate groups.
  • the PU is generally synthesized by preparing the prepolymer with terminal isocyanic groups , creating an aqueous emulsion through violent agitation and extending it with a suitable extender until the desired molecular weight is attained.
  • external emulsioning agents can be resorted to or prepolymers are prepared containing a fraction of polyoils with hydrophilic character and/or loaded with such groups, to obtain a polyurethane self-emulsifier prepolymer.
  • the best water emulsioned PU are those of aliphatic type, anionic obtained by contacting polyols and ionomers according to the correct ratios, enabling to resist to any severe treatment (acid ambient dying and basic reduction thereof, hot water and alkaline washing cycles.
  • External emulsifier can be ionic or non ionic surfactants, and are generally added in an amount ranging from 0.5% to 10% with respect to the PU.
  • self emulsifier PU are preferred which are obtained by means of groups which are progressively negatively charged, as dimetilolpropionic acid (DMPA) or functionalized sulfonic acids, forming a negatively charged emulsioned PU aqueous solution; said groups are added in a range 0,5 to 10% with respect to poliol concentration and are neutralized with triethylamine.
  • DMPA dimetilolpropionic acid
  • sulfonic acids forming a negatively charged emulsioned PU aqueous solution
  • cross-linkingagent varying from 0.5% to 8% can be added to the aqueous polyurethane solution used for impregnation, with the aim of reaching the desired physical-mechanical characteristics and solvent resistance; such reticulating, which can be melamines, aziridine, carbodiimide, epoxides, zirconium compounds, or isocyan bases are active in drying phase of the PU at a temperature that varies from 110°C to 180°C .
  • the polyurethane resin impregnated in the non-woven fabric is thermo-fixed to the same by drying, or is preliminarily coagulated and then dried; as an example, in the case of anionic type PU, coagulation can be carried out in an acidic aqueous solution, or, for a cationic PU, in an alkaline aqueous solution.
  • coagulation can be carried out in an acidic aqueous solution, or, for a cationic PU, in an alkaline aqueous solution.
  • the phase of implantation of the PU in the microfiber must happen in the shortest possible time, to avoid migration of the PU to the surface of the non-woven fabric, with consequent worsening of the chemical-physical characteristics and the aspect.
  • the H.S.PVA must be removed from the non-woven fabric, and this is done in a vibro-washer with warm water, at a temperature in the range 85° to 95°C; in case boric acid is added to H.S.PVA, the pH of the aqueous washing solution must be lowered to 3 to 5, while maintaining the temperature equally high.
  • the final piece is dried in warm air furnace and subjected to successive phases of working, which are, respectively, cutting in two along the section, emery polishing, dying and finishing.
  • the operating conditions of these productive stages reflect those used in the production of non-woven fabrics which use organic solvents.
  • a fiber is prepared in flocking formed from microfibers of PET (polyethyleneterphthalate) (0.13 to 0.15 denier) in a modified polyester matrix (TLAS), having the following characteristic:
  • the fiber is formed from 57 parts by weight of PET and 43 parts by weight of TLAS. If observed in section the fiber reveals the presence of 16 microfibers of PET embedded in the TLAS matrix.
  • a crude felt is prepared that is subjected to drawing in order to form a drawn felt with density 0.217 g/cc.
  • the drawn felt is re-emerged in warm water at a temperature of 90°C giving a density of 0,331 g/cc; this is then dipped in a 12% high saponification value polyvinylalcohol solution (H.S.PVA) at a temperature around 70°C and is thermo-fixed in a furnace at 150°C for 30 minutes.
  • the piece impregnated with PVA is dipped in a 10% solution of NaOH at a temperature of 60°C; the "sea" component dissolves in 18 minutes and in such conditions 8% of H.S.PVA is dissolved (see Table 1).
  • Example 1 Take a sample of felt impregnated and thermo-fixed with H.S.PVA as prepared in Example 1 and dissolve the "sea" component of the fiber by immersing it in a 5% solution of NaOH at a temperature of 60°C; the "sea” component dissolves in 20 minutes and in such conditions 15% of H.S.PVA is dissolved (see Table 1).
  • the experiments are programmed according to the logic of a Statistical Design Experiment and in particular of a Composed Central Design.
  • thermo-fixing at temperatures of 126°C, 130°C and 140°C, does not produce efficient Curing; therefore Curing must be carried out at high temperatures, higher than 150°C.
  • Figure 4 is a magnified representation of the fiber that shows the degree of migration (% migration of the PVA) of the distribution of the PVA along the thickness of the non-woven fabric after dissolving the "sea" component.
  • Example 17 The piece obtained in Example 17 in which the "sea" component has been dissolved has been impregnated with a solution of PU in aqueous emulsion (Witcobond 279-34: anionic, aliphatic, polyester basis polyurethane) from Baxenden Chemicals, at a concentration of 13,5%.
  • the piece is thermo-fixed for 30 minutes at a temperature of 160°C.
  • the piece is dried in an oven, cut in two in the section, buffed and dyed in a jet of dye.
  • the piece has a good surface appearance.
  • the chemical-physical characteristics and abrasion resistance are illustrated in Table 4.
  • Example 17 The piece obtained in Example 17 in which the "sea" component has been dissolved has been impregnated with a solution of PU in aqueous emulsion (Witcobond 279-34: anionic, aliphatic, polyether basis polyurethane) from Baxenden Chemicals, at a concentration of 12% in order to obtain 28% in the final product.
  • the piece is thermo-fixed for 30 minutes at a temperature of 160°C.
  • the piece is dried in an oven, cut in two in the section, buffed and dyed in a jet of dye.
  • the piece has a good surface appearance.
  • the chemical-physical characteristics and abrasion resistance are illustrated in Table 4.
  • Example 17 The piece obtained in Example 17 in which the "sea" component has been dissolved, has been impregnated with a solution of PU in aqueous emulsion (Witcobond 279-34: anionic, aliphatic, polyether basis polyurethane) from Baxenden Chemicals, in aqueous emulsion at a concentration of 13.5%, to which has been added 5% of capped isocyanic cross-linking.
  • the piece is thermo-fixed for 30 minutes at a temperature of 160°C.
  • the piece is dried in an oven, cut in two in the section, buffed and dyed in a jet of dye.
  • the piece has a good surface appearance.
  • the chemical-physical characteristics and abrasion resistance are illustrated in table 4.
  • EXAMPLE 29 (preparation of a microfibrous non-woven fabric) the piece obtained in Example 17 in which the "sea" component has been dissolved, has been impregnated with a solution of PU in aqueous emulsion (Witcobond 279-34: anionic, aliphatic, polyether basis polyurethane) from Baxenden Chemicals, in aqueous emulsion at a concentration of 13.5%, to which has been added 5% of capped isocyianiccross-linking.
  • the piece is thermo-fixed for 30 minutes at a temperature of 160°C.
  • the piece is dried in an oven, cut in two in the section, buffed and dyed in a jet of dye.
  • the piece has a good surface appearance.
  • the chemical-physical characteristics and abrasion resistance are illustrated in table 4.
  • EXAMPLE 30 (preparation of a microfibrous non-woven fabric) the piece obtained in Example 17 in which the "sea" component has been dissolved, has been impregnated with a solution of PU in aqueous emulsion (Impranil DLV: anionic, aliphatic, polyester basis polyurethane) from Bayer, in aqueous emulsion at a concentration of 13.5% in order to obtain 30% concentration in the final product, to which has been added 5% of capped isocyanic cross-linking agent.
  • the piece is thermo-fixed for 30 minutes at a temperature of 160°C.
  • the piece is dried in an oven, cut in two in the section, buffed and dyed in a jet of dye.
  • the piece has a good surface appearance.
  • the chemical-physical characteristics and abrasion resistance are illustrated in table 4.
  • aqueous emulsion Astacin Finish PF
  • the piece has a good surface appearance.
  • the chemical-physical characteristics and abrasion resistance are illustrated in table 4.
  • a felt is prepared according to the procedure of Example 1 in which the PET/TLAS ratio is 57/43 and the apparent density is 0.331.
  • the felt has been impregnated with a solution of PU (Witcobond aqueous emulsion containing 1% of boric acid) from Baxenden Chemicals) at a concentration of 85%, to which has been added 5% of cupped isocyanic agent.
  • the piece is thermo-fixed for 30 minutes at a temperature of 150°C.
  • the piece contains 24% of PVA which is three fourth of total PU (32%),.
  • the H.S.PVA previously applied in warm water is dissolved by treatment with a 10% sodium hydroxide water solution at a temperature of 60°C.
  • the piece is impregnated again with the above PU solution to obtain the sought PU concentration (32%) in the final product
  • the piece is dried in an oven, cut in two in the section, buffed and dyed in a jet of dye.
  • the piece has a good surface appearance.
  • the chemical-physical characteristics and abrasion resistance are illustrated in table 4.

Landscapes

  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Nonwoven Fabrics (AREA)
  • Synthetic Leather, Interior Materials Or Flexible Sheet Materials (AREA)
EP02004291A 2001-03-12 2002-02-28 Verfahren zur Herstellung eines mikrofasrigen, wildlederähnlichen Vliesstoffes ohne Verwendung organischer Lösungsmittel Expired - Lifetime EP1243691B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI010516 2001-03-12
IT2001MI000516A ITMI20010516A1 (it) 2001-03-12 2001-03-12 Processo per la produzione di un tessuto non tessuto microfibroso scamosciato senza l'uso di solventi organici

Publications (2)

Publication Number Publication Date
EP1243691A1 true EP1243691A1 (de) 2002-09-25
EP1243691B1 EP1243691B1 (de) 2008-09-17

Family

ID=11447230

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02004291A Expired - Lifetime EP1243691B1 (de) 2001-03-12 2002-02-28 Verfahren zur Herstellung eines mikrofasrigen, wildlederähnlichen Vliesstoffes ohne Verwendung organischer Lösungsmittel

Country Status (7)

Country Link
US (1) US6921508B2 (de)
EP (1) EP1243691B1 (de)
AT (1) ATE408727T1 (de)
DE (1) DE60228907D1 (de)
ES (1) ES2312500T3 (de)
IT (1) ITMI20010516A1 (de)
PT (1) PT1243691E (de)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1760177A1 (de) * 2004-06-17 2007-03-07 Kuraray Co., Ltd. Verfahren zur herstellung aus miteinander verschlungenen ultrafeinen filamenten
ITMI20121780A1 (it) * 2012-10-22 2014-04-23 Alcantara Spa Nuovo processo per la preparazione di un tessuto non tessuto micro fibroso sintetico scamosciato
EP2896741A1 (de) * 2012-09-14 2015-07-22 Toray Industries, Inc. Verfahren zur herstellung eines bahnförmigen objekts und in diesem verfahren hergestelltes bahnförmiges objekt
KR20150090122A (ko) * 2012-11-30 2015-08-05 도레이 카부시키가이샤 시트상물 및 그 시트상물의 제조 방법

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ATE437264T1 (de) 2002-04-10 2009-08-15 Alcantara Spa Verfahren zur herstellung eines mikrofasrigen, wildlederähnlichen vliesstoffes
US8075904B2 (en) * 2004-08-11 2011-12-13 California Institute Of Technology High aspect ratio template and method for producing same for central and peripheral nerve repair
US7837913B2 (en) * 2004-08-11 2010-11-23 California Institute Of Technology High aspect ratio template and method for producing same
US20100215895A1 (en) * 2005-08-10 2010-08-26 Reliance Industries Ltd. Process of producing ultra fine microdenier filaments and fabrics made thereof
WO2015038860A2 (en) * 2013-09-13 2015-03-19 Federal-Mogul Powertrain, Inc. High surface area fiber and method of construction thereof
CN110886095B (zh) * 2018-09-07 2022-05-20 安安(中国)有限公司 一种雪花绒合成革生产方法
CN111962309B (zh) * 2020-08-27 2022-10-11 晋江旭华新材料科技有限公司 一种水性聚氨酯定岛超细纤维复合片材的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3731352A (en) * 1970-06-15 1973-05-08 Toray Industries Method of manufacturing a fibrous sheet
US4206257A (en) * 1977-11-28 1980-06-03 Kuraray Co., Ltd. Napped sheet material bearing the characteristics of a suede-leather and method of producing the same
JPS61215782A (ja) * 1985-03-15 1986-09-25 Toray Ind Inc 人工皮革シ−トの製造方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3531368A (en) * 1966-01-07 1970-09-29 Toray Industries Synthetic filaments and the like
US3899623A (en) * 1972-04-10 1975-08-12 Toray Industries Synthetic leather combination of needle-punched fabric and polyetherester polyurethane
JPS5834592B2 (ja) * 1973-03-09 1983-07-27 東レ株式会社 チヨウビキユ−ナチヨウオリモノノ セイホウ
JPS6043472B2 (ja) * 1981-12-15 1985-09-28 東レ株式会社 高耐久性立毛布帛の製造方法
DE3345071A1 (de) * 1983-12-13 1985-06-20 Bayer Ag, 5090 Leverkusen Hitzevernetzbare pur-beschichtungsmassen, verfahren zu ihrer herstellung und ihre verwendung
JP2980261B2 (ja) * 1991-07-23 1999-11-22 株式会社クラレ 繊維シート状物の製造方法
CA2277077C (en) * 1997-11-07 2009-03-24 Toray Industries, Inc. Nubuck-like artificial leather and a production process thereof
US6322851B1 (en) * 1998-06-30 2001-11-27 Kuraray Co., Ltd. Manufacturing process for leather-like sheet
US6284680B1 (en) * 1998-11-17 2001-09-04 Japan Vilene Company Nonwoven fabric containing fine fibers, and a filter material
TWI223019B (en) * 1999-03-16 2004-11-01 Kuraray Co Artificial leather sheet substrate and production process thereof
US6479153B1 (en) 1999-03-30 2002-11-12 Kuraray Co., Ltd. Process for producing a leather-like sheet
TW526303B (en) * 2000-01-06 2003-04-01 Kuraray Co Artificial leather shoe and artificial leather suited therefor
JP4350258B2 (ja) * 2000-03-14 2009-10-21 株式会社クラレ 染色性に優れた軽量繊維

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3731352A (en) * 1970-06-15 1973-05-08 Toray Industries Method of manufacturing a fibrous sheet
US4206257A (en) * 1977-11-28 1980-06-03 Kuraray Co., Ltd. Napped sheet material bearing the characteristics of a suede-leather and method of producing the same
JPS61215782A (ja) * 1985-03-15 1986-09-25 Toray Ind Inc 人工皮革シ−トの製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 011, no. 053 (C - 404) 19 February 1987 (1987-02-19) *

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1760177A4 (de) * 2004-06-17 2008-10-15 Kuraray Co Verfahren zur herstellung aus miteinander verschlungenen ultrafeinen filamenten
US8178184B2 (en) 2004-06-17 2012-05-15 Kuraray Co., Ltd. Process for producing intertwined ultrafine filament sheet
EP1760177A1 (de) * 2004-06-17 2007-03-07 Kuraray Co., Ltd. Verfahren zur herstellung aus miteinander verschlungenen ultrafeinen filamenten
EP2896741A1 (de) * 2012-09-14 2015-07-22 Toray Industries, Inc. Verfahren zur herstellung eines bahnförmigen objekts und in diesem verfahren hergestelltes bahnförmiges objekt
US10301770B2 (en) 2012-09-14 2019-05-28 Toray Industries, Inc. Process for producing sheet-shaped material and sheet-shaped material obtained by said process
EP2896741A4 (de) * 2012-09-14 2016-06-08 Toray Industries Verfahren zur herstellung eines bahnförmigen objekts und in diesem verfahren hergestelltes bahnförmiges objekt
CN104854273A (zh) * 2012-10-22 2015-08-19 阿尔坎塔拉股份公司 制备非织造微纤维绒面革状合成织物的方法
KR20150084866A (ko) * 2012-10-22 2015-07-22 알칸타라 에스.피.에이. 극세사 스웨이드-유사 합성 부직포의 제조 방법
JP2015536388A (ja) * 2012-10-22 2015-12-21 アルカンタラ、ソシエタ、ペル、アチオニＡｌｃａｎｔａｒａ Ｓ．Ｐ．Ａ． スエード状マイクロファイバー合成繊維不織布の生成方法
WO2014087271A1 (en) 2012-10-22 2014-06-12 Alcantara S.P.A. Process for the preparation of a non-woven microfibrous suede-like synthetic fabric
RU2635607C2 (ru) * 2012-10-22 2017-11-14 Алькантара С.П.А. Способ получения синтетической микроволокнистой нетканой ткани под замшу
ITMI20121780A1 (it) * 2012-10-22 2014-04-23 Alcantara Spa Nuovo processo per la preparazione di un tessuto non tessuto micro fibroso sintetico scamosciato
US10400391B2 (en) 2012-10-22 2019-09-03 Alcantaea S.P.A. Process for the preparation of a non-woven microfibrous suede-like synthetic fabric
KR20150090122A (ko) * 2012-11-30 2015-08-05 도레이 카부시키가이샤 시트상물 및 그 시트상물의 제조 방법
US20150315741A1 (en) * 2012-11-30 2015-11-05 Toray Industries, Inc. Sheet-shaped material and process for producing said sheet-shaped material (as amended)
EP2927368A4 (de) * 2012-11-30 2016-06-29 Toray Industries Folienförmiges objekt und verfahren zur herstellung des folienförmigen objekts

Also Published As

Publication number Publication date
ES2312500T3 (es) 2009-03-01
ATE408727T1 (de) 2008-10-15
ITMI20010516A1 (it) 2002-09-12
DE60228907D1 (de) 2008-10-30
PT1243691E (pt) 2008-12-10
US20030017773A1 (en) 2003-01-23
US6921508B2 (en) 2005-07-26
EP1243691B1 (de) 2008-09-17

Similar Documents

Publication Publication Date Title
EP1353006B1 (de) Verfahren zur Herstellung eines mikrofasrigen, wildlederähnlichen Vliesstoffes
EP0833005B1 (de) Wildlederartiges Kunstleder
US6921508B2 (en) Method for the production of microfibrous suede-finish non-woven fabric without using organic solvents
RU2635607C2 (ru) Способ получения синтетической микроволокнистой нетканой ткани под замшу
JP2004533561A (ja) 合成スエード革およびその製造方法
KR100625110B1 (ko) 폴리우레탄함침 스웨이드조 인공피혁의 제조방법
CN1316119C (zh) 微纤麂皮非织造布的生产工艺及相关方法
EP3574139B1 (de) Mehrfaseriger mehrschichtiger verbundstoff für anwendungen im kraftfahrzeugsektor
EP1300508A2 (de) Verfahren zur Herstellung eines mikrofasrigen Vliesstoffes mit Filz-Aussehen und einer Flor-freien Oberfläche
KR20040054558A (ko) 멜란지형 외관을 갖는 고내구성 부직포, 그의 제조 방법및 상기 제조 방법에 적합한 장치
EP0082013B1 (de) Bindemittel für Polgewebe sowie Verfahren zur Herstellung von Polgeweben
KR20020039598A (ko) 극세사 편성물을 이용한 스웨드조 인공피혁의 제조방법
KR100337990B1 (ko) 누박조인공피혁의제조방법
JPH07197383A (ja) 伸縮性合成皮革の製造方法
KR100221602B1 (ko) 인공피혁
KR100231325B1 (ko) 누박조 인공피혁의 제조방법
US20030024053A1 (en) Method for boiling-off of blended fabric from polyamide fiber and polyurethane fiber, method for producing dyed blended fabric and dyed blended fabric
JPS5940948B2 (ja) スエ−ド調人工皮革の製造方法
JP3844093B2 (ja) ポリウレタン弾性糸含有繊維製品の処理方法
JPS6238476B2 (de)
JPS6131235B2 (de)
JPH07173717A (ja) 電気植毛用パイル原糸

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20021224

AKX Designation fees paid

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

17Q First examination report despatched

Effective date: 20061219

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60228907

Country of ref document: DE

Date of ref document: 20081030

Kind code of ref document: P

REG Reference to a national code

Ref country code: PT

Ref legal event code: SC4A

Free format text: AVAILABILITY OF NATIONAL TRANSLATION

Effective date: 20081126

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080917

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080917

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2312500

Country of ref document: ES

Kind code of ref document: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080917

26N No opposition filed

Effective date: 20090618

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080917

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090228

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090228

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090228

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090228

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081217

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20081218

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20090228

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080917

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20080917

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 15

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 16

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 17

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PT

Payment date: 20210209

Year of fee payment: 20

Ref country code: NL

Payment date: 20210223

Year of fee payment: 20

Ref country code: FR

Payment date: 20210223

Year of fee payment: 20

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20210317

Year of fee payment: 20

Ref country code: GB

Payment date: 20210223

Year of fee payment: 20

Ref country code: DE

Payment date: 20210225

Year of fee payment: 20

Ref country code: BE

Payment date: 20210224

Year of fee payment: 20

REG Reference to a national code

Ref country code: DE

Ref legal event code: R071

Ref document number: 60228907

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: MK

Effective date: 20220227

REG Reference to a national code

Ref country code: BE

Ref legal event code: MK

Effective date: 20220228

REG Reference to a national code

Ref country code: GB

Ref legal event code: PE20

Expiry date: 20220227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20220227

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20220309

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20220624

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION

Effective date: 20220301